Cycloalkanone or alkyl aryl ketone assisting cationic dye and aromatic polyamide dyeing therewith

ABSTRACT

A DYE ASSISTANT FOR AROMATIC POLYAMIDE FIBROUS MATERIAL IS SHOWN. THE DYE ASSISTANT COMPRISES WITHER A CYCLIC ALIPHATIC KETONE SUCH AS CYCLOHEXANONE OR AN ARYL KETONE SUCH AS ACETOPHENONE. A METHOD OF DYEING SUCH AROMATIC POLYAMIDE MATERIAL WHICH INCLUDES THE DYE ASSISTANT SET FORTH HEREINABOVE IS ALSO SHOWN. THE METHOD INCLUDES THE STEPS OF IMMERSING THE FIBER IN A DYE BATH INCLUDING WATER, A SURFACTANT, AND THE DYE ASSISTANT OF THE INVENTION AND THENCE PRESSURRIZING THE BATH AND RAISING THE TEMPERATURE THEREOF UNTIL THE DYEING IS COMPLETED.

United States Patent 3,674,420 CYCLOALKANONE 0R ALKYL ARYL KETONE AS- SISTING CATIONIC DYE AND AROMATIC POLYAMIDE DYEING THEREWITH Ira Sapers, Maplewood, N.J., assignor to Arkansas Company, Inc., Newark, NJ. No Drawing. Filed Oct. 22, 1969, Ser. No. 868,566

Int. (:1. D06}: 5/04 U.S. c1. s-173 5 Claims ABSTRACT OF THE DISCLOSURE A dye assistant for aromatic polyamide fibrous material is shown. The dye assistant comprises either a cyclic aliphatic ketone such as cyclohexanone or an aryl ketone such as acetophenone.

A method of dyeing such aromatic polyamide material which includes the dye assistant set forth hereinabove is also shown. The method includes the steps of immersing the fiber in a dye bath including water, a surfactant, and the dye assistant of this invention and thence pressurizing the bath and raising the temperature thereof until the dyeing is completed.

DESCRIPTION OF THE INVENTION This invention relates to dye assistants for aromatic polyamide fibrous material and to methods of dyeing such material.

Recently aromatic polyamides have become an important synthetic fiber. These aromatic polyamides consist, for example, of a condensation product of an aromatic diamine with an aromatic diacid halide. Examples of such condensation products are, for example, types 430 and 450 Nomex, made by E. I. du Pont de Nemours & Co. and other similar fibers.

Fibrous material of the above type makes excellent fabrics. These fabrics, contrary to other fabrics made of condensation-type polyamides such as type 6/6 nylon, melt at a very high temperature and even if brought to a temperature above their char point, will not propagate a flame.

Unfortunately fibrous material of this type has not yet become important in fabric manufacture. This is due to the fact that no proper method has heretofore been de veloped to dye such fibrous material. Obviously, undyed fibrous material of this type is completely unsatisfactory for making most articles of clothing and, what is even worse, some of the variations of aromatic polyamide fibrous material have a normally dirty brownish color.

It has been heretofore proposed to make such fibrous material dyeable by adding a dye-attracting group to the structure of the material such as, for example, a sulfonic acid radical or the like. Unfortunately, while the addition of such a group will cause the fibrous material to become dyeable, the strength of the fiber becomes so seriously reduced as to make it unsatisfactory for use in wearing apparel.

I have discovered that aromatic polyamide fibrous material, without the addition of dye-attracting groups, can become dyeable by the use of the specific types of dye assistants as set forth in this specification. The use of these dye assistants will cause satisfactory dyeing to be produced with the use of conventional dyeing equipment. The color fastness, light fastness, and other dye properties of the dyed material are fully comparable with the prop erties of conventional dyed material.

A dye assistant comprises either a cycloalkyl ketone, such as cyclohexanone or a phenyl alkyl ketone such as acetophenone.

3,674,420 Patented July 4, 1972 "Ice The preferred proportion of the dye assistant to dye bath is five percent by weight. However, these percentages can be considerably reduced (to as \low as one percent, for example, when light shades are being dyed) and can range as high as fifteen percent by weight. Cationic dyes are preferred for use in this invention. The preferred percentage will depend upon the specific dye used. Naturally, for economic reasons, the smallest quantity of dye assistant that will be satisfactory for the purpose is used.

In order to improve the levelling of the dye upon the fibrous material, it is also desirable to use a surfactant. The surfactant used can be either a cationic surfactant, a nonionic plus an anionic surfactant, or a non-ionic plus a cationic surfactant. An example of a cationic surfactant that can be employed is coconut trimethyl ammonium chloride, an example of an anionic surfactant that can be employed is a nonyl phenoxy ethanoxy ammonium sulfate. Examples of nonionic surfactants that can be employed are nonyl phenol reacted with 30 mols of ethylene oxide and Pluronic P-68 which is a block copolymer of polypropylene oxide and ethylene oxide. The molecular weight of polypropylene oxide is 1750 and the polyethylene oxide constitutes 80% of the weight of the copolymer. See Pat. No. 2,674,619 and The New Expanded Pluronic Acid and Typical Physical publication by the Wyndotte Chemical Companies.

The invention also includes the method of dyeing the aromatic polyamide fibrous material. The method includes the steps of immersing the fibrous material in a dye bath which includes water, surfactant and the dye assistant of this invention, agitating the fibrous material in the bath until the materials are well distributed therein, and thence pressurizing and raising the temperature of the bath until the dyeing is completed.

There are further surprising results that are accomplished by the addition of other components to the dyeing assistant system of this invention.

For example, acetophenone is one of the compounds set forth in the generalized formula of the dyeing assistant of this invention. Likewise, cyolohexanone is also a compound falling within this generalized formula. If a composition is made which includes these two components, there are far superior dyeing results produced than those produced with one of the elements alone. Furthermore, with the cyclohexanone-acetophenone combination, more even and level dyeing results, and excess dyeing assistant can be more easily washed out of the material.

Even better results are accomplished by the addition of swelling agents to the compositions, such as, for example, di-methyl sulfoxide, n-methyl 2 pyrrolidone, butyrolactone, n,n-di-methyl acetamide, and n,n-di-methy1 formamide.

In the specific composition of acetophenone, cyclohexanone and surfactants, the preferred proportions are fiftytwo percent (52%) acetophenone, forty-six percent (46%) cyclohexanone and two percent (2%) of the surfactant. These proportions can be varied to as low as twenty-five percent (25% by weight of acetophenone and seventy-five percent by weight of cyclohexanone, or alternatively, twenty-five percent (25%) by weight of cyclohexanone and seventy-five percent (75 by weight of acetophenone. The surfactant percentages may range from one percent (1%) to five percent (5%) by weight.

Where swelling agents are included in the compositions, the range of percentages are from five (5%) percent to forty (40%) percent by Weight. Preferably swelling agents, where utilized, should amount to about twenty percent (20%) of the composition.

The invention will now be further described by specific examples of the practice thereof.

Example 1 A relatively heavy fabric composed of 100% of Type 430 Nomex fibrous material (manufactured by E. I. du Pont de Nemours & Co.) [weight 250 lbs] prescoured and de-sized, was placed within a dye bath at 100 the bath having a composition consisting of an intimate mixture of the following:

Lbs.

Water 5000 Acetic acid (56%) 2.5 Salt ('NaCl) 5D Acetophenone 244 Pluronic F-68 6 The material was worked in the bath for a period of five to ten minutes. Thereafter 10 lbs. of pre-dissolved Astrazon Olive Green BL (a cationic dye manufactured by Verona Dyestuffs) and described on page S176 of the Colour Index Second Edition 1956, Supplement 1963, published by The Society of Dyers and Colourists Dean House, Piccadilly, Bradford, Yorkshire, England, as a Quinoline Dye, C.I. Basic Green 6, was added to the bath and the fabric worked in the bath for an additional five to ten minutes. The dyeing equipment used was conventional pressure dyeing equipment. The dye bath was capable of being sealed hermetically but was open while the above treatment was being carried out. The covers were then placed on the bath and the bath was sealed hermetically. The bath was heated to a temperature of 270 F. and maintained at that temperature for approximately two hours. The bath was then cooled to 190 F, the seals released slowly to depressurize the bath and the covers removed. The bath was then overflowed with hot water at 150 F. and then dropped and the fabric was then rinsed with warm water at 110 F. for a period of about twenty minutes. The fabric was then after-scoured, as follows:

An after-scouring bath was prepared at a temperature of 140 F. having the following ingredients:

Lbs.

Water 5000 A non-ionic surfactant consisting of nonyl-phenol reacted with 30 mols of ethylene oxide 2 /2 Tetra sodium pyrophosphate 5 The above bath was heated to 180 F. and the fabric was run in the bath from twenty to thirty minutes. The bath was then overflowed and dropped and the fabric rinsed with warm water at 110 F. for fifteen minutes. The fabric was then rinsed with water at room temperature (80 F.) for an additional fifteen minutes. The wet fabric was then spun to remove the excess water and was then dried. An excellent color fast dye was produced.

Example II A relatively heavy fabric consisting entirely of Type 450 Nomex fibers (manufactured by E. I. du Pont de Nemours & Company) and which weighed about 250 pounds, was previously pre-scoured and de-sized and then placed within a dye bath having the following composition:

. Lbs. Water 5000 Acetic acid (56%) 2 /2 Salt (NaCl) 100 Pluronic F-68 5 Cyclohexanone 185.6 Acetophenone 62.5

The dyeing procedures used were the same as set forth in Example 1 and the dye used was also Astrazon Olive Green BL C.I. Basic Green 6. After dyeing the material was after-scoured using the same procedures as set forth in Example 1. An excellent dyeing was produced.

Example III A relatviely heavy fabric consisting entirely of Type 450 Nomex fibrous material previously pre-scoured (Manufactured by E. I. du Pont de Nemours & Company) [weight 250 lbs] was de-sized and placed within a dye bath maintained at a temperature of F. The bath had the following composition:

Lbs.

Water 5000 Acetic acid (56%) 2 /2 Salt (NaCl) n-Methyl-Z-pyrrolidone 22.5 di-methyl sulfoxide 22.5 Acetophenone 1 75 Cyclohexanone 25 Pluronic F-68 5 The bath was maintained within conventional pressure dyeing equipment. The components of the bath were thoroughly mixed with the bath uncovered. The material was worked in the bath for a period of five to ten minutes. Thereafter ten pounds of .pre-dissolved Astrazon Orange 3RL (a cationic dye manufactured by Verona Dyestuffs) and described in the Colour Index Second Edition 1956, Supplement 1963, published by The Society of Dyers and Colourists Dean House, Piccadilly, Bradford, Yorkshire, England, on page $156 as a Methine Dye, C.I. Basic Orange 27, was added to the bath and the fabric worked in the uncovered bath for an additional ten minutes. Thereafter, covers were placed on the bath and the bath sealed hermetically. The bath was then heated to a temperature of 250 and maintained at that temperature for approximately two and one-half hours. The bath was then cooled to 190 F., the seals released slowly to depressurize the bath and the covers removed. The bath was then overflowed with hot water at 150 F. and the fabric then rinsed with warm water at F. for a period of about thirty minutes. Thereafter, the same after-scouring, spinning and drying proc ess as described in Example 1 were applied An excellent shade of orange was produced.

The foregoing sets forth the manner in which the objects of this invention are achieved.

I claim:

1. A dyeing composition comprising a cationic dye and a dye assistant, said composition being adapted for use in the dyeing of synthetic fibers made of aromatic polyamide material, said dye assistant being selected from the class consisting of cycle-alkyl ketones and phenyl alkyl ketones.

2. A dyeing composition comprising a cationic dye and a dye assistant, said composition being adapted for use in the dyeing of synthetic fibers made of aromatic polyamide material, said dye assistant being selected from the class consisting of acetophenone and cyclohexanone.

3. A dyeing composition comprising a cationic dye and a dye assistant, said composition being adapted for use in the dyeing of synthetic fibers made of aromatic polyarnide material, said dye assistant being composed of acetophenone.

4. A method of dyeing aromatic polyamide fibers comprising the steps of immersing said fibers in a bath consisting of water, a surfactant, a cationic dye and a dye assistant, said dye assistant consisting of a compound selected from the class consisting of cyclo-alkyl ketones and phenyl alkyl ketones, thence pressurizing said bath and raising the temperature thereof until the dyeing is completed.

5. A method of dyeing aromatic polyamide fibers comprising the steps of immersing said fibers in a bath consisting of Water, a surfactant, a cationic dye and a dye 6 assistant, said dye assistant consisting of a compound OTHER REFERENCES selected from the class consisting of acetophenone and cyclohexanone, thence pressurizing said bath and rais- 1963 coljumn 6511e' ing the temperature thereof until the dyeing is completed. Shmldlen: Preparatlon and 'Dyelng of Synthetic Flbres,

5 pp. 150-157. References Cited UNITED STATES PATENTS DONALD LEVY, Primary Examiner 3,184,436 5/1965 Magat 260-78 3,232,910 2/1966 Preston 260-78 3,506,990 4/1970 Richardson 8-172 10 s 172 

